KR20200062027A - Block copolymer composition, method for preparing the block copolymer composition, and asphalt composition comprising the block copolymer composition - Google Patents

Abstract

The present invention relates to a block copolymer composition. More specifically, the present invention relates to: a block copolymer composition, in which, in a block copolymer composition comprising a diblock copolymer and a triblock copolymer, the diblock copolymer comprises a first block comprising a repeating unit derived from a first conjugated diene-based monomer and a second block comprising a repeating unit derived from a first vinyl aromatic monomer, and comprises a functional group derived from a modified initiator represented by chemical formula 1 (see description of the invention) at one end of the diblock copolymer; a manufacturing method thereof, and an asphalt composition comprising the block copolymer composition. When the block copolymer composition according to the present invention is used as an asphalt modifier, there is an effect of simultaneously improving the softening point and solubility of the asphalt composition to excellent levels.

Description

Block copolymer composition, method for manufacturing the same, and asphalt composition including the same

The present invention relates to a block copolymer composition, and more particularly, to a block copolymer composition for use as an asphalt modifier, a manufacturing method thereof, and an asphalt composition comprising the same.

Asphalt is a residue after most of the volatile oil in the petroleum oil component evaporates, and maintains a highly viscous liquid or semi-solid at high temperatures, but has properties of hardening at temperatures below room temperature. In addition, since asphalt is rich in plasticity, has great waterproofness, electrical insulation, adhesiveness, and has chemically stable characteristics, it is widely applied to building materials such as road pavement and waterproofing materials. However, such asphalt has a problem that plastic deformation occurs when exposed to high temperatures for a long time during use, and cracks are generated by external impacts at low temperatures.

In order to solve such a problem, studies have recently been conducted to improve asphalt properties by adding various polymers.

For example, there is a method of using a vinyl aromatic hydrocarbon-conjugated diene copolymer, such as a styrene-butadiene-styrene (SBS) copolymer, as a modifier or impact modifier that improves the properties of an asphalt composition.

 In general, in order to use the SBS copolymer in the asphalt composition, compatibility with asphalt is the most basic and essential.

However, due to the recent increase in the crude oil price of petroleum and the energy saving policy, the refinery facility is continuously being upgraded, and the content of asphaltene, a by-product in the refinery residue asphalt, is increasing. Since the asphaltene is an aggregate of aromatic hydrocarbons and contains a lot of polar functional groups at the ends, the compatibility with SBS copolymer without polar functional groups is very low. Therefore, not only the processing time of the asphalt composition is greatly increased, but also the degradation of the quality of the asphalt, such as a decrease in elasticity of the modified asphalt composition.

To solve this problem, a method of adjusting the molecular weight of the SBS copolymer or changing the molecular microstructure of the SBS copolymer so as to add a coupling effect, or a method of adding an additive such as oil as a processing aid Although it has been proposed, it is not the ultimate solution because individual prescriptions must be made for each asphalt with various quality variations.

Therefore, there is an urgent need to develop an SBS copolymer as an asphalt modifier having excellent compatibility with asphalt.

KR 0711270 B1

The problem to be solved in the present invention, in order to solve the problems mentioned in the technology that is the background of the invention, the softening point of the asphalt composition, including a diblock copolymer terminal-modified in the block copolymer composition used as an asphalt modifier And improving solubility at the same time.

That is, the present invention is to provide a block copolymer composition usable as an asphalt modifier, and when modifying the asphalt using the block copolymer composition, an object of the present invention is to provide an asphalt composition with improved softening point and solubility.

According to an embodiment of the present invention for solving the above problems, the present invention is a block copolymer composition comprising a diblock copolymer and a triblock copolymer, the diblock copolymer is a first conjugated diene-based monomer A block comprising a first block comprising a derived repeating unit and a second block comprising a repeating unit derived from a first vinyl aromatic monomer, and a functional group derived from a modified initiator represented by Formula 1 below at one end of the diblock copolymer Provided is a copolymer composition.

[Formula 1]

In Chemical Formula 1, R ₁ is a hydrocarbyl group having 1 to 20 carbon atoms, R ₂ is an alkylene group having 1 to 30 carbon atoms, and R ₃ and R ₄ are each independently hydrogen or 1 to 30 carbon atoms. It is an alkyl group.

In addition, the present invention, in the presence of a denaturation initiator represented by the formula (1), preparing a first block comprising a repeating unit derived from a first conjugated diene-based monomer; Preparing a diblock copolymer by polymerizing a second block including a repeating unit derived from a first vinyl aromatic monomer in the presence of the first block prepared in the above step; Preparing a triblock copolymer; And it provides a method for producing a block copolymer composition comprising the step of mixing the diblock copolymer and the triblock copolymer.

 [Formula 1]

In Chemical Formula 1, R ₁ is a hydrocarbyl group having 1 to 20 carbon atoms, R ₂ is an alkylene group having 1 to 30 carbon atoms, and R ₃ and R ₄ are each independently hydrogen or 1 to 30 carbon atoms. It is an alkyl group.

In addition, the present invention provides an asphalt composition comprising the block copolymer composition and asphalt.

When the block copolymer composition according to the present invention is used as an asphalt modifier, it has an effect of simultaneously improving the softening point and solubility of the asphalt composition to excellent levels.

Terms or words used in the description and claims of the present invention should not be construed as being limited to ordinary or lexical meanings, and the inventor appropriately explains the concept of terms in order to best explain his or her invention in the best way. Based on the principle of being able to be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

In the present invention, the terms'derived repeating unit','derived functional group' and'derived linking group' may refer to a component, structure, or the substance itself originating from a substance, and in a specific example,'derived repeating unit' is a polymerization of a polymer At this time, the monomer to be introduced may mean a repeating unit formed in the polymer by participating in the polymerization reaction, and'derived functional group' refers to a repeating unit formed in the polymer by participating in the polymerization reaction during the polymerization of the polymer. It may mean a functional group connected to one end, and'derived linking group' means a linking group that connects each polymer in the coupled polymer by introducing the coupling agent into the coupling reaction during the coupling reaction between the polymers. May be

In the present invention, the term'block' may mean a group of repeating units composed of only repeating units derived from the same monomer, only the same monomers participating in the polymerization reaction in the copolymer, and specific examples include repeating units derived from vinyl aromatic monomers. The block may mean a block formed of only repeating units derived from a vinyl aromatic monomer, and a block including a repeating unit derived from a conjugated diene-based monomer may mean a block formed only of repeating units derived from a conjugated diene-based monomer. .

In the present invention, the terms'diblock copolymer' and'triblock copolymer' may mean a copolymer comprising two or more blocks derived from different monomers.

In the present invention, the term'active polymer' is a polymer formed by an anionic polymerization reaction, and one end of the polymer may mean a polymer capable of additional polymerization or reaction by maintaining an anionic state, and specifically, a living anionic polymer. have.

In the present invention, the term'solution' is in the form of dispersing or dissolving polymers, diblock copolymers and block copolymers produced by polymerization or coupling reaction of each step of the method for preparing a block copolymer composition in a hydrocarbon-based solvent. It can mean what it contains.

<Block copolymer composition>

The block copolymer composition according to the present invention may include a diblock copolymer and a triblock copolymer.

In general, the vinyl aromatic-conjugated diene block copolymer mainly used as an asphalt modifier, especially in the styrene-butadiene-styrene (SBS) triblock copolymer, the content between the styrene block and the butadiene block, the vinyl group present in the conjugated diene block Factors related to the microstructure of molecules, such as the content of, are correlated with each other, and when the high temperature property increases, the low temperature property decreases, when the dissolution rate increases, the mechanical property decreases, and when the sulfur is crosslinked, a gel is formed in the asphalt composition Can cause problems. However, the block copolymer composition according to the present invention includes a triblock copolymer and a diblock copolymer containing a functional group derived from a modified initiator at one end at the same time, so that an additive is added or the molecular weight of the triblock copolymer is adjusted. Or, there is an effect of improving the softening point and solubility without changing the molecular microstructure.

The diblock copolymer included in the block copolymer composition according to the present invention includes a first block comprising a repeating unit derived from a first conjugated diene-based monomer and a second block comprising a repeating unit derived from a first vinyl aromatic monomer, , It may be to include a functional group derived from a modified initiator represented by the following formula (1) at one end of the diblock copolymer. Meanwhile, the one end may be one end of the first block of the diblock copolymer.

[Formula 1]

In Chemical Formula 1, R ₁ is a hydrocarbyl group having 1 to 20 carbon atoms, 1 to 15 carbon atoms, or 2 to 8 carbon atoms, and R ₂ is 1 to 30 carbon atoms, 1 to 20 carbon atoms, and 1 to 20 carbon atoms. It is an alkylene group having 8 carbon atoms, and R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or an alkyl group having 1 to 8 carbon atoms.

The first block including the repeating unit derived from the first conjugated diene-based monomer of the diblock copolymer may be a block formed by polymerization of the first conjugated diene-based monomer. The first conjugated diene-based monomer for forming the first block is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2 It may be one or more selected from the group consisting of -phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom). The content of the repeating unit derived from the first conjugated diene-based monomer may be 60 parts by weight to 80 parts by weight, 65 parts by weight to 75 parts by weight, or 67 parts by weight to 73 parts by weight based on 100 parts by weight of the total diblock copolymer have. When using a block copolymer composition containing a diblock copolymer within this range as an asphalt modifier, there is an effect of improving the softening point and solubility of the asphalt composition.

Further, the second block including the repeating unit derived from the first vinyl aromatic monomer of the diblock copolymer may be a block formed by polymerization of the first vinyl aromatic monomer. The first vinyl aromatic monomer for forming the second block is styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- It may be one or more selected from the group consisting of (p-methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene. The content of the repeating unit derived from the first vinyl aromatic monomer may be 20 parts by weight to 40 parts by weight, 25 parts by weight to 35 parts by weight, or 27 parts by weight to 33 parts by weight based on 100 parts by weight of the diblock copolymer. . When using a block copolymer composition containing a diblock copolymer within this range as an asphalt modifier, there is an effect of improving the softening point and solubility of the asphalt composition.

On the other hand, in order to further improve the softening point and solubility of the asphalt composition comprising the diblock copolymer composition, one end of the diblock copolymer, specifically, the modification represented by Formula 1 below at one end of the first block And initiator-derived functional groups.

[Formula 1]

In Chemical Formula 1, R ₁ is a hydrocarbyl group having 1 to 20 carbon atoms, 1 to 15 carbon atoms, or 2 to 8 carbon atoms, and R ₂ is 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 1 carbon atom It is an alkylene group having 8 carbon atoms, and R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or an alkyl group having 1 to 8 carbon atoms.

As a specific example, the denaturation initiator represented by Formula 1 may be represented by Formula 2 and Formula 3 below.

[Formula 2]

[Formula 3]

The denaturation initiator of the functional group derived from the denaturation initiator may be a denaturation initiator prepared by denaturation with a benzyl amine compound in order to improve the softening point and solubility of the asphalt composition. When the functional group derived from the benzyl amine-based compound is located at one end of the diblock copolymer, the affinity between the polar group present in the asphalt and the functional group derived from the denaturation initiator increases, and thus the asphalt of the diblock copolymer containing the same There is an effect to improve the solubility. The improved solubility of the diblock copolymer also has an effect of improving the overall solubility of the block copolymer composition because it also aids in chain relaxation of the triblock copolymer contained together in the block copolymer composition. In addition, after the diblock copolymer is dissolved in asphalt, a reaction between functional groups derived from the benzyl amine-based compound in the diblock copolymer may occur due to the high temperature (180° C. or higher) inside the asphalt. The block copolymer is modified in the form of a triblock copolymer or a combination of several diblock copolymers, thereby increasing the polymer content and contributing to the improvement of physical properties. Therefore, when using a block copolymer containing a diblock copolymer containing a functional group derived from the modified initiator at one end as an asphalt modifier, there is an effect of improving the softening point and solubility of the asphalt composition.

In addition, the modified initiator may be a vinyl group substituted among benzyl amine-based compounds, which not only serves to initiate the polymerization reaction during the preparation of the diblock copolymer, but also hydrogen between functional groups derived from the modified initiator in the final step of the reaction. Interactions such as gelation, including binding, covalent bonding, and the like can be performed.

That is, the modified initiator according to the present invention serves as an initiator, and the terminal of the diblock copolymer prepared using the same can be effectively modified. Therefore, even without the introduction of a coupling agent, in the modified asphalt production process, the form of a triblock copolymer or a combination of several diblock copolymers is modified according to the interaction between the functional groups derived from the modified initiator, thereby increasing the polymer content and contributing to improving physical properties. It works. Accordingly, there is an excellent effect of compatibility with the components included in the asphalt composition and the softening point of the asphalt composition.

The content of the functional group derived from the denaturation initiator is. The diblock copolymer may be 0.248 parts by weight to 0.322 parts by weight, 0.248 parts by weight to 0.32 parts by weight, or 0.25 parts by weight to 0.3 parts by weight based on 100 parts by weight of the total. When using a block copolymer composition containing a diblock copolymer within this range as an asphalt modifier, there is an effect of improving the softening point and solubility of the asphalt composition.

The triblock copolymer included in the block copolymer composition according to the present invention is derived from a third block including a repeating unit derived from a second vinyl aromatic monomer, a fourth block including a repeating unit derived from a second conjugated diene monomer, and a coupling agent. It may include a linker.

The third block including the repeating unit derived from the second vinyl aromatic monomer of the triblock copolymer may be a block formed by polymerization of the second vinyl aromatic monomer. The second vinyl aromatic monomer for forming the third block is styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- It may be one or more selected from the group consisting of (p-methylphenyl)styrene and 1-vinyl-5-hexylnaphthalene, and may be the same or different from the first vinyl aromatic monomer described above. The content of the repeating unit derived from the second vinyl aromatic monomer may be 20 parts by weight to 40 parts by weight, 25 parts by weight to 35 parts by weight, or 27 parts by weight to 33 parts by weight based on 100 parts by weight of the triblock copolymer have. When using a block copolymer composition containing a triblock copolymer within this range as an asphalt modifier, there is an effect of improving the softening point and solubility of the asphalt composition.

In addition, the fourth block including the repeating unit derived from the second conjugated diene-based monomer of the triblock copolymer may be a block formed by polymerization of the second conjugated diene-based monomer. The second conjugated diene-based monomer for forming the fourth block is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2 -Phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom) may be at least one selected from the group consisting of, the same as the first conjugated diene monomer described above or It can be different. The content of the repeating unit derived from the second conjugated diene-based monomer may be 60 parts by weight to 80 parts by weight, 65 parts by weight to 75 parts by weight, or 67 parts by weight to 73 parts by weight based on 100 parts by weight of the triblock copolymer. . When using a block copolymer composition containing a triblock copolymer within this range as an asphalt modifier, there is an effect of improving the softening point and solubility of the asphalt composition.

The coupling agent-derived linking group may be a linking group connecting a block including a repeating unit derived from a plurality of second conjugated diene-based monomers. The coupling agent for forming the coupling group derived from the coupling agent may be at least one selected from the group consisting of a vinyl group-containing hydrocarbon-based compound, an ester-based compound, a silane-based compound, a polysiloxane-based compound, and a polyketone. As a specific example, the coupling agent is a polyfunctional coupling agent, a vinyl group-containing hydrocarbon-based compound such as divinylbenzene; Ester-based compounds such as diethyl adipate and glycidyl methacrylate; Silane compounds such as dimethyldichlorosilane, methyldichlorosilane, methoxysilane, glycidoxy trimethoxysilane, and oxydipropyl bis(trimethoxysilane); polysiloxane compounds such as α, ω-bis(2-trichlorosilylethyl)polydimethylsiloxane; Or it may be one or more selected from the group consisting of polyketone. The content of the coupling group derived from the coupling agent may be 0.278 parts by weight to 0.516 parts by weight, 0.28 parts by weight to 0.51 parts by weight, or 0.285 parts by weight to 0.45 parts by weight based on 100 parts by weight of the total triblock copolymer. Within this range, the coupling efficiency increases, and when a block copolymer composition including a triblock copolymer is used as an asphalt modifier, there is an effect of improving the softening point of the asphalt composition.

On the other hand, with respect to the total content of the block copolymer composition, the content of the diblock copolymer may be 25 wt% to 42 wt%, 30 wt% to 40 wt%, or 30 wt% to 35 wt%, and the tree The content of the block copolymer may be 58% to 75% by weight, 60% to 70% by weight, and 65% to 70% by weight. When the block copolymer composition is used as an asphalt modifier within this range, there is an effect of improving the softening point and solubility of the asphalt composition.

At this time, the coupling efficiency of the block copolymer composition may be 62% to 79%, 62% to 73%, or 65% to 67%, within this range the block copolymer composition according to the present invention as an asphalt modifier It has the effect of improving the softening point and solubility of the asphalt composition.

<Method for preparing block copolymer composition>

According to the present invention, a method for preparing the block copolymer composition may be provided. Method for producing a block copolymer composition according to the present invention comprises the steps of preparing a diblock copolymer; Preparing a triblock copolymer; And mixing the diblock copolymer and the triblock copolymer.

The preparing of the diblock copolymer may include preparing a first block including a repeating unit derived from a first conjugated diene-based monomer in the presence of a denaturing initiator represented by Formula 1; And in the presence of the first block prepared in the step, polymerizing a second block including a repeating unit derived from a first vinyl aromatic monomer to prepare a diblock copolymer.

[Formula 1]

In Chemical Formula 1, R ₁ is a hydrocarbyl group having 1 to 20 carbon atoms, 1 to 15 carbon atoms, or 2 to 8 carbon atoms, and R ₂ is 1 to 30 carbon atoms, 1 to 20 carbon atoms, and 1 to 20 carbon atoms. It is an alkylene group having 8 carbon atoms, and R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, 1 to 20 carbon atoms, or an alkyl group having 1 to 8 carbon atoms.

The modified initiator may be used by preparing a modified initiator represented by Formula 1 by reacting a polymerization initiator with a vinyl group-substituted benzyl amine compound.

As a specific example, in the formula (1), R ₁ is derived from a butyl group, and R ₂ is a methylene group, R ₃ and R ₄ are methyl groups, respectively. When N,N-dimethyl vinylbenzyl amine is used as a starting material and reacted with n-butyllithium, which is a polymerization initiator, the n-butyllithium is substituted at one end to form an benzyl amine compound as an active polymer.

[Formula 2]

In another specific example, in Formula 1, when R ₁ is derived from a butyl group, and R ₂ is a methylene group, R ₃ and R ₄ are each hydrogen, the modification initiator is as follows. When a vinyl benzyl amine is used as a starting material, and reacted with n-butyllithium, which is a polymerization initiator, the n-butyllithium is substituted at one end to form an active polymer benzyl amine compound.

 [Formula 3]

As the polymerization initiator, in addition to n-butyl lithium, methyl lithium, ethyl lithium, propyl lithium, s-butyl lithium, t-butyl lithium, hexyl lithium, n-decyl lithium, t-octyl lithium, phenyl lithium, 1-naphthyl lithium , n-ethylsilicium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium, lithium Alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, lithium isopropylamide and the like can be used.

Preparation of the denaturation initiator according to the present invention is carried out for 5 minutes to 20 minutes, 5 minutes to 15 minutes, or 7 minutes to 12 minutes at a temperature of 50 ℃ to 70 ℃, 53 ℃ to 68 ℃ or 58 ℃ to 62 ℃ Can be. Within this range, the reaction rate of the polymerization initiator and the vinyl group-substituted benzyl amine-based compound is fast, thereby facilitating the preparation of a modified initiator.

The molar ratio of the starting material and the polymerization initiator during the reaction for preparing the modified initiator may be 1:0.7 to 1.1 1:0.75 to 1.1 or 1:0.8 to 1.1. Within this range, the reaction rate of the polymerization initiator and the vinyl group-substituted benzyl amine-based compound is fast, thereby facilitating the preparation of a modified initiator.

In the step of preparing the first block, in a hydrocarbon solvent, in the presence of the denaturing initiator, a first conjugated diene-based monomer is added and polymerized to include a first monoblock polymer comprising a repeating unit derived from the first conjugated diene-based monomer. It may be a step of preparing a solution. The first monoblock polymer solution prepared in the step of preparing the first block includes a polymer for forming a block including a repeating unit derived from a first conjugated diene-based monomer.

The step of preparing the diblock copolymer by polymerizing the second block comprises: a first monoblock polymer solution comprising a repeating unit derived from the first conjugated diene-based monomer prepared in the step of preparing the first block, the first By adding and polymerizing a vinyl aromatic monomer, a first diblock copolymer solution comprising a first block comprising a repeating unit derived from a first conjugated diene monomer and a second block comprising a repeating unit derived from a first vinyl aromatic monomer is obtained. It may be a manufacturing step. Since the polymer for forming a block is a living anionic polymer in which an end of the polymer is anionically active by polymerization, the step of preparing the diblock copolymer by polymerizing the second block may be performed without input of a separate polymerization initiator. . That is, the second block is polymerized by a first vinyl aromatic monomer that is additionally injected from the living anionic polymer, followed by a repeating unit block derived from the first conjugated diene-based monomer, followed by a first input when polymerizing the second block. It may be a step for preparing a first diblock copolymer solution including a first diblock copolymer, in which a block according to a vinyl aromatic monomer is formed.

In the step of preparing the triblock copolymer, in a hydrocarbon solvent, a third block including a repeating unit derived from a second vinyl aromatic monomer, a fourth block including a repeating unit derived from a second conjugated diene monomer, and a coupling group derived from a coupling agent It may be to include a step of preparing a triblock copolymer comprising.

The step of preparing the triblock copolymer may be performed separately from the step of preparing the diblock copolymer, and may be performed simultaneously or sequentially with the diblock copolymer.

The triblock copolymer includes a repeating unit derived from a second vinyl aromatic monomer by adding and polymerizing a second vinyl aromatic monomer in the presence of a common polymerization initiator that can be used in the art, in a hydrocarbon solvent. Preparing a second monoblock polymer solution comprising a third block forming polymer; A second conjugated diene-based monomer is added to the polymer solution for forming a third block including a repeating unit derived from a second vinyl aromatic monomer prepared in the step of preparing the second monoblock polymer solution, and then polymerized to obtain a second vinyl aromatic Preparing a second diblock copolymer solution comprising a second diblock copolymer comprising a third block comprising a repeat unit derived from a monomer and a fourth block comprising a repeat unit derived from a second conjugated diene-based monomer; And a third block comprising a repeating unit derived from a second vinyl aromatic monomer, by adding a coupling agent to the second diblock copolymer solution prepared in the step of preparing the second diblock copolymer solution, and performing a coupling reaction. It may be carried out including the step of preparing a triblock copolymer comprising a fourth block comprising a repeating unit derived from a second conjugated diene-based monomer and a coupling group derived from a coupling agent.

In the step of preparing the second monoblock polymer solution, a polymerization unit of a triblock copolymer initiates polymerization to form a third block comprising a repeating unit derived from a second vinyl aromatic monomer, and a repeating unit derived from a second vinyl aromatic monomer. It may be a step for preparing a second monoblock polymer solution comprising a polymer for forming a third block comprising a. The second monoblock polymer solution prepared in the step of preparing the second monoblock polymer solution may include a polymer for forming a block including a repeating unit derived from a second vinyl aromatic monomer.

In addition, the step of preparing the second diblock copolymer solution comprises a repeating unit derived from the second vinyl aromatic monomer contained in the second monoblock polymer solution prepared in the step of preparing the second monoblock polymer solution. 3 In the presence of a polymer for forming a block, a second conjugated diene-based monomer is added and polymerized to form a third block comprising a repeating unit derived from a second vinyl aromatic monomer and a fourth block comprising a repeating unit derived from a second conjugated diene-based monomer. It may be a step for preparing a second diblock copolymer solution comprising a second diblock copolymer comprising blocks. The second monoblock polymer solution prepared in the step of preparing the second monoblock polymer solution includes a polymer for forming a repeating unit block derived from a second vinyl aromatic monomer, which is the step of preparing the previous second monoblock polymer solution. Since the end of the polymer by polymerization is an anionic active living anionic polymer, the step of preparing the second diblock copolymer can be carried out without input of a separate polymerization initiator. That is, in the step of preparing the second diblock copolymer, a polymerization reaction of a second conjugated diene-based monomer that is additionally introduced from the living anionic polymer is performed, and a third block including a repeating unit derived from a second vinyl aromatic monomer Subsequently, a block according to the second conjugated diene-based monomer input in the step of preparing the second diblock copolymer may be a step for preparing the second diblock copolymer.

In addition, in the step of preparing the triblock copolymer, the second diblock copolymer contained in the second diblock copolymer solution prepared in the step of preparing the second diblock copolymer is coupled using a coupling agent. By ring reaction, the diblock copolymer may be a step for preparing a solution comprising a triblock copolymer coupled, that is, a block copolymer. The second diblock copolymer solution prepared in the step of preparing the second diblock copolymer comprises a second diblock copolymer, which is copolymerized by polymerization in the step of preparing the second diblock copolymer. Since the terminal, specifically, the terminal of the block containing the repeating unit derived from the second conjugated diene monomer is an anionic active living anionic copolymer, the number of functional groups that can be substituted or added to the coupling agent can be added. Accordingly, a coupling reaction in which the functional group of the second coupling agent is replaced with the living anionic copolymer or the living anionic copolymer is added to the functional group of the second coupling agent may be performed. That is, in the triblock copolymer, a second diblock copolymer may be connected by the coupling agent according to the number of functional groups that can be substituted or added in a coupling agent, and specific examples include two or more second diblocks. The copolymer may be coupled by a coupling group derived from the coupling agent, and more specifically, 2 to 4 second diblock copolymers may be coupled by a coupling group derived from the coupling agent.

In addition, the step of preparing the triblock copolymer may further include, after the coupling reaction, removing the activity of the active polymer by adding water or alcohol into the reactor.

According to the present invention, the hydrocarbon-based solvent does not react with a polymerization initiator, and can be used as long as it is usually used for anionic polymerization reactions. Specific examples include butane, n-pentane, n-hexane, n-heptane or iso-octane. Linear or branched aliphatic hydrocarbon compounds; Cyclic aliphatic hydrocarbon compounds unsubstituted or substituted with alkyl groups such as cyclopentane, cyclohexane, cycloheptane, methyl cyclohexane or methyl cycloheptane; And it may be an aromatic hydrocarbon compound unsubstituted or substituted with an alkyl group such as benzene, toluene, xylene or naphthalene, any one of them, or a mixture of two or more.

Further, the polymerization initiator used in the step of preparing the block copolymer may be one or more selected from the polymerization initiators described above.

The step of mixing the diblock copolymer and the triblock copolymer may be a step for preparing a block copolymer composition in which the diblock copolymer and the triblock copolymer are mixed with each other. The mixing may be carried out by mixing in the form of a powder, respectively, in order to evenly distribute and distribute the diblock copolymer and the triblock copolymer in the block copolymer composition, respectively, comprising the diblock copolymer prepared in the above step It can be carried out by mixing the solution and the solution containing the triblock copolymer prepared in the above step, in this case, the dispersibility of the diblock copolymer and the triblock copolymer is excellent, and has a uniform distribution, block air There is an excellent effect of balance between the physical properties of the asphalt composition containing the coalescence composition.

<Asphalt composition>

According to the present invention, an asphalt composition comprising an asphalt modifier for the block copolymer composition is provided. The asphalt composition may include the block copolymer composition and asphalt. At this time, the block copolymer composition may be included in 1 part by weight to 10 parts by weight, 3 parts by weight to 8 parts by weight, or 4 parts by weight to 6 parts by weight based on 100 parts by weight of the total asphalt composition, within this range The block copolymer composition has excellent solubility in asphalt, and has an excellent effect in the physical properties of the asphalt composition.

The asphalt composition may further include a crosslinking agent for crosslinking the asphalt composition. The crosslinking agent may be a sulfur compound containing sulfur or iron sulfate, a specific example may be a sulfur element (powder), and the crosslinking agent may be included in an amount of 0.05 to 3 parts by weight based on 100 parts by weight of the total asphalt composition, It maintains an appropriate crosslinking reaction within this range, improves high temperature properties and elasticity, and has an effect of preventing gelation.

In addition, the asphalt may include asphaltenes in an amount of 1 wt% to 40 wt%, or 5 wt% to 30 wt% based on the total weight of the asphalt.

In addition, the asphalt composition may be a road pavement material, or a building material such as a waterproof material.

Hereinafter, the present invention will be described in more detail by examples. However, the following examples are intended to illustrate the present invention, and it is apparent to those skilled in the art that various changes and modifications can be made within the scope and technical scope of the present invention, and the scope of the present invention is not limited thereto.

Example

Example 1

<Production of diblock copolymer>

After 4440 g of cyclohexane and 1.965 g of N,N-dimethyl vinylbenzyl amine were dissolved in a high-pressure reactor substituted with nitrogen, the temperature was raised to 60°C. When the reactor temperature reached 60° C., 25.44 g of n-butyl lithium diluted to 4% was added to cyclohexane. At this time, the solution had an anionic group and turned red. A solution containing a denaturation initiator represented by the following Chemical Formula 2 was prepared by stirring for 10 minutes. Subsequently, 612 g of 1,3-butadiene was added to the solution containing the prepared denaturation initiator, and the butadiene block was polymerized while stirring. When all butadiene monomers are exhausted, 238 g of styrene is added to the mixed solution in which the butadiene block is generated, polymerization is performed until styrene is completely consumed, and 10 g of water is added as a reaction terminator to remove the reaction activity. , A diblock copolymer solution including a (butadiene)-(styrene) diblock copolymer substituted with a functional group derived from a modified initiator represented by the following Chemical Formula 2 was prepared.

[Formula 2]

<Triblock copolymer production>

4440 g of purified cyclohexane and 238 g of styrene were added to a 10 L reactor substituted with nitrogen and heated to 60°C while stirring. When the reactor temperature reached 60°C, 25.44 g of n-butyllithium diluted with 4% in cyclohexane was added to the reactor to polymerize the styrene block.

Subsequently, when all of the styrene was consumed, 612 g of 1,3-butadiene was added to polymerize until 1,3-butadiene was completely consumed to prepare (styrene)-(butadiene) diblock copolymer.

After completion of the polymerization reaction, 0.77 g of dimethyldichlorosilane was added as a coupling agent to the mixed solution in which (styrene)-(butadiene) diblock copolymer was produced, under conditions of 105°C and 3.5 bar, and the coupling reaction was performed for 5 minutes. Was carried out. Subsequently, 1 g of water was added as a reaction terminator to remove the reaction activity, and a triblock copolymer solution including a triblock copolymer to which (styrene)-(butadiene) diblock copolymer was coupled was prepared. At this time, the coupling efficiency was 92.89%.

<Preparation of block copolymer composition>

33 parts by weight of the prepared diblock copolymer solution (based on solid content) and 67 parts by weight of the prepared triblock copolymer solution (based on solid content) were mixed for 10 hours, and the mixed solution was stripped, coagulated, and dried to block air Copolymer composition pellets were prepared.

Example 2

In Example 1, when preparing the diblock copolymer, instead of 1.965 g of N,N-dimethyl vinylbenzyl amine, 1.965 g of vinyl benzyl amine (primary amine) was added to prepare a solution containing a modified initiator represented by Formula 3 below. It was carried out in the same manner as in Example 1, except that it was prepared.

[Formula 3]

Example 3

In Example 1, when preparing the block copolymer composition, except that the diblock copolymer solution was used as 48 parts by weight instead of 33 parts by weight (based on solid content), instead of 52 parts by weight of triblock copolymer solution (based on solid content) Was carried out in the same manner as in Example 1.

Example 4

In Example 1, when manufacturing the block copolymer composition, except that the diblock copolymer solution was used as 33 parts by weight (based on solids) instead of 16 parts by weight, triblock copolymer solution 67 parts by weight (based on solids) instead of 84 parts by weight Was carried out in the same manner as in Example 1.

Comparative Example 1

In Example 1, when the block copolymer composition was prepared, the triblock copolymer solution was not used, and the diblock copolymer solution was used in the same manner as in Example 1, except that only 100 parts by weight (based on solids) was used. Did.

Comparative Example 2

In Example 1, when the block copolymer composition was prepared, the diblock copolymer solution was not used, and the triblock copolymer solution was used in the same manner as in Example 1, except that only 100 parts by weight (based on solids) was used. Did.

Comparative Example 3

<Triblock copolymer production>

4440 g of purified cyclohexane and 238 g of styrene were added to a 10 L reactor substituted with nitrogen and heated to 60°C while stirring. When the reactor temperature reached 60° C., 28.54 g of n-butyllithium diluted with 4% in cyclohexane was added to the reactor to polymerize the styrene block.

Subsequently, when all of the styrene was consumed, 612 g of 1,3-butadiene was added to polymerize until 1,3-butadiene was completely consumed to prepare (styrene)-(butadiene) diblock copolymer.

After completion of the polymerization reaction, 1.003 g of dimethyldichlorosilane was added as a coupling agent to the mixed solution in which (styrene)-(butadiene) diblock copolymer was produced, under conditions of 105°C and 3.5 bar, and the coupling reaction was performed for 5 minutes. Was carried out. Subsequently, 1 g of water was added as a reaction terminator to remove the reaction activity, and a triblock copolymer solution including a triblock copolymer coupled with (styrene)-(butadiene) diblock copolymer was prepared. At this time, the coupling efficiency is shown in Table 1 below.

Comparative Example 4

In Comparative Example 3, when the triblock copolymer was prepared, Comparative Example 3 was used except that 26.05 g instead of 28.54 g of n-butyllithium diluted to 4% in cyclohexane and 0.75 g of 1.003 g of dimethyldichlorosilane were used. It was carried out in the same way.

Comparative Example 5

In Comparative Example 3, when the triblock copolymer was prepared, it was carried out in the same manner as in Comparative Example 3, except that 0.90 g was used instead of 1.003 g of dimethyldichlorosilane.

Comparative Example 6

In Comparative Example 3, when the triblock copolymer was prepared, Comparative Example 3 was used except that 28.54 g of n-butyllithium diluted in cyclohexane at 4% was used as 23.67 g, and 0.85 g instead of 1.003 g of dimethyldichlorosilane. It was carried out in the same way.

Experimental Example

Experimental Example 1

TSV viscosity (cSt), maximum peak molecular weight (Mp, X 10 ³ g/mol), coupling efficiency (C/E, %) of each block copolymer composition prepared in Examples 1 to 4 and Comparative Examples 1 to 6 ) And the content of the repeating unit derived from the styrene monomer and the content of the repeating site derived from the vinyl monomer in the block copolymer composition are shown in Table 1 below.

In addition, when using each block copolymer composition prepared in Examples 1 to 4 and Comparative Examples 1 to 6 as an asphalt modifier, to compare the softening point, viscosity and phase separation temperature, asphalt at 180° C. (SK AP-5 ) 600 g of each block copolymer composition prepared in Examples 1 to 4 and Comparative Examples 1 to 6 was calculated and added at 4.5% by weight, and then 30 minutes at 2,500 rpm in a high shear stirrer (HSM, High Shear Mixer). After mixing for a while, the mixture was stirred for 2 hours at 250 rpm in a low shear stirrer (LSM, Low Shear Mixer), and the softening point, viscosity, and phase separation temperature (solubility) were measured and shown in Table 1 below.

* TSV viscosity (cSt): The block copolymer composition was dissolved in toluene at a concentration of 5% by weight and measured using a capillary viscometer in a constant temperature bath maintained at 25°C.

* Maximum peak molecular weight (Mp, X 10 ³ g/mol), coupling efficiency (%), styrene monomer-derived repeat unit content and vinyl monomer-derived repeat unit content: PLgel Olexis (Polymer Laboratories) two columns and PLgel mixed- G permeation chromatograph (GPC) was measured by combining a single column of C (Polymer Laboratories), and when calculating the maximum peak molecular weight, the GPC standard material was performed using polystyrene (PS), a repeating unit derived from styrene monomer. The content and the repeating unit content derived from vinyl monomer were measured through the GPC and 1H NMR. The coupling efficiency was calculated and expressed based on the following Equation 1 using the peak area of the polymer shown in GPC.

[Equation 1]

Coupling efficiency (%) = {(area of coupled polymer)/(area of entire polymer)} X 100

* Softening point (℃): As the asphalt composition specimen, according to ASTM D36, when the water or glycerin is heated at 5 °C per minute, the specimen starts to soften by this, and beads with a diameter of 9.525 mm and a weight of 3.5 g are placed on the specimen 1 The temperature when sagging by inches was measured.

* Viscosity (cps): When preparing the asphalt composition, after 2 hours of low-shear stirring, the viscosity of 135° C. was measured using a Brookfield Viscometer (BROOK FIELD VISCOMETER).

* Phase separation temperature (solubility △T, ℃): 50 g of the prepared asphalt composition is improved in an aluminum tube, aged in an oven at 180° C. for 72 hours (aging), and then divided into three parts to determine the softening point of the upper and lower parts. It was measured in the same way. At this time, the lower the value of the phase separation temperature means that the solubility increases.

division Example Comparative example One 2 3 4 One 2 3 4 5 6 TSV viscosity (cSt) 14.04 14.06 12.80 17.50 7.382 18.19 14.05 14.12 12.81 17.55 SBS Mp (X 10 ³ g/mol) 126.3 126.5 125.270 122.030 - 121.902 109.750 113.205 107.031 120.450 SB Mp (X 10 ³ g/mol) 65.536 66.12 67.22 69.432 65.318 69.609 58.731 61.507 58.282 67.340 C/E (%) 67.44 66.44 50.20 83.25 - 92.89 86.96 68.23 82.82 82.84 styrene
(weight%) 28.4 28.5 28.5 28.4 28.4 28.65 28.9 28.7 29.1 28.5 Vinyl (% by weight) 17.0 17.1 17.4 17.2 17.0 17.6 19.0 17.5 16.04 17.1 Softening point (℃) 87.1 87.0 89.5 88.1 68.0 92.5 85.8 86.1 85.4 88.0 Viscosity (cps) 2,385 2410 2,250 2,420 1545 2590 2,260 2,275 2,112 2,415 Phase separation temperature
(△T) 0.9 1.6 4.2 3.9 0.1 27 0.2 11 4.2 13

As shown in Table 1, the example using the block copolymer composition comprising the diblock copolymer and the triblock copolymer according to the present invention as an asphalt modifier was confirmed to be excellent in both softening point and solubility.

On the other hand, it was confirmed that Comparative Example 1 containing only the diblock copolymer had a lower softening point, and Comparative Example 2 containing only the triblock copolymer had a lower solubility.

In addition, as a case of using a diblock copolymer that does not contain a functional group derived from the modified initiator represented by the formula (1), a block copolymer composition prepared by mixing a diblock copolymer and a triblock copolymer is a comparative example In the case of 3 to 6, it can be seen that the softening point is reduced (Comparative Examples 3 and 5) or the solubility confirmed at the phase separation temperature is reduced compared to the examples according to the present invention (Comparative Examples 4 and 6).

Claims (12)

In the block copolymer composition comprising a diblock copolymer and a triblock copolymer,
The diblock copolymer includes a first block including a repeating unit derived from a first conjugated diene-based monomer and a second block including a repeating unit derived from a first vinyl aromatic monomer,
Block copolymer composition comprising a functional group derived from a modified initiator represented by the following formula (1) at one end of the diblock copolymer:
[Formula 1]

In Chemical Formula 1, R ₁ is a hydrocarbyl group having 1 to 20 carbon atoms, R ₂ is an alkylene group having 1 to 30 carbon atoms, and R ₃ and R ₄ are each independently hydrogen or 1 to 30 carbon atoms. It is an alkyl group. According to claim 1,
The block copolymer composition, a block copolymer composition comprising 25% to 42% by weight of the diblock copolymer, and 58% to 75% by weight of the triblock copolymer. According to claim 1,
The block copolymer composition, the block copolymer composition comprising 30% to 35% by weight of the diblock copolymer, and 65% to 70% by weight of the triblock copolymer. According to claim 1,
R ₁ is a C 2 to C 8 hydrocarbyl group, R ₂ is a C 1 to C 8 alkylene group, and R ₃ and R ₄ are each independently hydrogen or a C 1 to C 8 alkyl block copolymer. Composition. According to claim 1,
The modified copolymer represented by Chemical Formula 1 is a modified block copolymer composition represented by Chemical Formula 2 or Chemical Formula 3.
[Formula 2]

[Formula 3]

According to claim 1,
The triblock copolymer is a block copolymer composition comprising a third block comprising a repeating unit derived from a second vinyl aromatic monomer, a fourth block comprising a repeating unit derived from a second conjugated diene monomer, and a coupling group derived from a coupling agent. According to claim 1,
The block copolymer composition has a coupling efficiency of 62% to 79%. According to claim 1,
The block copolymer composition has a coupling efficiency of 65% to 67%. Preparing a first block comprising a repeating unit derived from a first conjugated diene-based monomer in the presence of a denaturation initiator represented by Formula 1;
Preparing a diblock copolymer by polymerizing a second block including a repeating unit derived from a first vinyl aromatic monomer in the presence of the first block prepared in the above step; And
Preparing a triblock copolymer; And
Method for producing a block copolymer composition comprising the step of mixing the diblock copolymer and the triblock copolymer:
[Formula 1]

In Chemical Formula 1, R ₁ is a hydrocarbyl group having 1 to 20 carbon atoms, R ₂ is an alkylene group having 1 to 30 carbon atoms, and R ₃ and R ₄ are each independently hydrogen or 1 to 30 carbon atoms. It is an alkyl group. The method of claim 9,
The block copolymer composition is a block copolymer composition production method comprising 25% to 42% by weight of the diblock copolymer and 58% to 75% by weight of the triblock copolymer. An asphalt composition comprising the block copolymer composition according to any one of claims 1 to 8 and asphalt. The method of claim 11,
The block copolymer composition is an asphalt composition comprising 1 part by weight to 10 parts by weight based on 100 parts by weight of the asphalt composition.